O-cyanoaryl alkylphosphonothioates



United States Patent 3,131,120 O-CYANQARYL ALKYLPHQSPHSNGTIHGATES John P. Chupp, Kirkwood, and Peter E. Newailis, Crest- Wood, Mo, assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Dec. 19, 1961, Ser. No. 160,634 17 Claims. (61. 167-30) This invention relates to novel O-cyanoaryl alkylphosphonothioates and to methods of making same. Additionally this invention relates to pesticidal compositions containing the aryl alkylphosphonothioates of this invention as an active ingredient.

The O-cyanoaryl alkylphosphonothioates of this invention can be represented by the formula S ON wherein n is an integer from 0 to 1, wherein R is a lower alkyl radical (e.g., methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof containing up to carbon atoms), and wherein R is an aromatic hydrocarbon radical of the benzene series containing 6 to carbon atoms (e.g., phenyl, tolyl, xylyl, ethylpheny-l, cumyl, tert-butylphenyl, and the various isomeric forms thereof). In general n will be zero, R will be methyl or ethyl but usually methyl, and R will be phenyl or tolyl but usually phenyl.

The method of invention comprises reacting a cyanophenol of the formula wherein n has the aforedescribed significance with an alkylphosphonohalidothionate of the formula wherein R and R have the aforedescribed significance and wherein Z is a halogen of atomic number in the range of 16 to 36 (i.e., chlorine or bromine, usually chlorine) in the presence of hydrogen halide scavenging agent (e.g., sodium carbonate, potassium carbonate, the tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, dimethylaniline, lu-tidine, l-pipecoline, pyridine, etc.) in an amount at least sufiicient to absorb the hydrogen halide by-product. The scavenging agent can be added at the beginning of the reaction or throughout the course of the reaction. While a wide range of reaction temperatures can be employed provided the system is fluid (i.e., a reaction temperature above the freezing point of the system up to and including the boiling point of the system) it is preferred to employ a reaction temperature in the range of about 20 C. to about 120 C. Where and when desired an inert organic solvent (e.g., benzene, xylene, toluene, acetone, butanone, dioxane, etc.) can be used. Ordinarily the respective reactants will be employed in substantially equimolecular proportions.

As illustrative of cyanophenol reactants of the preferred process of this invention are Z-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-cyano-4-methylphenol, 2-cyano-3- methylphenol, 3-cyano-4-methylphenol, 2-methyl-4-cyanophenol, 3-methyl-4-cyanophenol, etc. As illustrative of 3,l3l,l2 Patented Apr. 28, 196

ice

alkylphosphonohalidothionate reactants of the preferred process of this invention are O-phenyl methylphosphonochloridothionate,

O-phenyl ethylphosphonochloridothionate,

O-phenyl n-propy-lphosphoncchloridothionate,

O-phenyl isoamylphosphonobromidothionate,

O-(p tolyl) methylphosphonochloridothionate,

O-(m-tolyl) methylphosphonochloridothionate,

O-(o-tolyl) ethylphosphonochloridothionate,

O-(p-cumyl) methylphosphonobromidothionate,

O-(p-t-butylphenyl) methylphcsphonochloridothionate,

etc.

As illustrative of the preferred method of this invention but not limitative thereof is the following:

Example I To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged approximately 132 parts by weight of benzene, approximately 6.0 parts by weight (substantially 0.05 mole) of 4-cyanophenol, approximately 6.1 parts by weight (substantially 0.06 mole) of tniethylamine, and approximately 10.4 parts by weight (substantially 0.05 mole) of O-phenyl methylphosphonochloridothionate. While agitating the mixture is heated up to the reflux temperature and then refluxed for 5 hours. The reaction mass is then cooled to room temperature and then quenched with water. The organic layer is separated and washed first with aqueous 3% sodium carbonate and then with water. The so-washed solution is then stripped of volatiles under vacuum. The residue, a cream-colored solid melting at 7374 C., is O-phenyl O-(4-cyanophenyl) mcthylphosphonothioate.

Example 11 Employing the procedure of Example I but replacing 4-cyanophenol with an equimolecular amount of Z-cyanophenol there is obtained O-phenyl O-(Z-cyanophenyl) methylphosphoncthioate which is insoluble in water.

Example III To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged approximately 176 parts by weight of benzene, approximately 6.0 parts by weight (substantially 0.05 mole) of 4-cyanophenol, approximately 6.1 parts by weight (substantially 0.06 mole) of triethylamme, and approximately 11.0 parts by weight (substantially 0.05 mole) of O-(-tolyl) methylphosphonochloridothionate. While agitating the mixture is heated up to the reflux temperature and then refluxed for 5 hours. The reaction mass is then cooled to room temperature and then quenched with water. The organic layer is separated and Washed first with aqueous 3% sodium carbonate and then with water. The so-washed solution is then stripped of volatiles under vacuum. The residue is O-(o-tolyl) O-(4-cyanophenyl) methylphosphonothioate.

Example IV Employing the procedure of Example 111 but replacing O-(o-tolyl) methylphosphonochloridothionate with an equimolecular [amount of O-(otolyl) ethylphosphonobromidothionate there is obtained O-(o-tolyl) O-(4-cyanophenyl) ethylphosphonothioate which is soluble in water.

Example V To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged approximately 176 parts by weight of benzene, approximately 6.0 parts by weight (substantially 0.05 mole) of 4-cyanophe- 1101, approximately 6.1 parts by weight (substantially 0.6 mole) of triethylamine, and approximately 11.0 parts by Employing the procedure of Example V but replacing 4-cyanophenol with an equirnolecular amount of 3- methyl-4-cyanophenol there is obtained O-(m-tolyl) O- (3-methyl-4-cyanophenyl) methylphosphonothioate which is insoluble in water.

Example VII To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged approximately 176 parts by weight of benzene, approximately 6.0 parts by weight (substantially 0.05 mole) of 4-cyanophenol, approximately 6.1 parts by weight (substantially 0.06 mole) of triethylamine, and approximately 10.4 parts by weight (substantially 0.05 mole) of O-(p-tolyl) methylphosphonochloridothionate. While agitating the mixture is heated up to the reflux temperature and then refluxed for 6 hours. The reaction mass is then cooled to room temperature and then quenched with water. The organic layer is separated and washed first with aqueous 3% sodium carbonate and then with water. The sowashed solution is then stripped of volatiles under vacuum. The residue is O-(p-tolyl) O-(4-cyanophenyl) methylphosphonothioate.

Example VIII Employing the procedure of Example VII but replacing O-(p-tolyl) methylphosphonochloridothionate with an equimolecular amount of O-(m-terL-butylphenyl) isoamylphosphonobromidothionate there is obtained O(mtert.-butylphenyl) O-(4-cyanophenyl) isoamylphosphonothioate.

Example IX To a suitable reaction vessel equipped with a thermom eter, agitator and reflux condenser is charged approximately 176 parts by weight of benzene, approximately 6.0 parts by weight (substantially 0.05 mole) of 4-cyan0- phenol, approximately 6.1 parts by weight (substantially 0.06 mole) of triethylamine, and approximately 11.5 parts by weight (substantially 0.05 mole) of O-phenyl ethylphosphonochloridothionate. While agitating the mixture is heated up to the reflux temperature and then refluxed for 6.5 hours. The reaction mass is then cooled to room temperature and then quenched with Water. The organic layer is separated and washed first with aqueous 3% sodium carbonate and then with Water. The sowashed solution is then stripped of volatiles under vacuum. The residue is O-phenyl O-(4-cyanopheny-l) ethylphosphonothioate.

Example X However, the product is generally satisfactory for insecticidal purposes without further purification.

4 As illustrative of other alkylphosphonothioates of this invention are O-phenyl O-(4-cyanophenyl) n-prop-ylphosphonothioate O-phenyl O-(4-cyanophenyl) isoarnylphosphonothioate O-phenyl O-(Z-cyanophenyl) n-propylphosphonothioate O-phenyl O=(3-methyl-4-cyanophenyl) methylphosphonothioate O-phenyl O-(4-methyl-2-cyanophenyl) methylphosphonothioate O-(m-tolyl) O-(2-cyanophenyl) methylphosphonothioate O-(o-tolyl) O-(4-cyanophenyl) n-propylphosphonothioate O-(o-tert.-butylphenyl) O-(4-cyanophenyl) methylphosphonothioate O-phenyl O- (3cyanophenyl) methylphosphonothioate O-(m-tolyl) O-(4-cyanophenyl) ethylphosphonothioate Of the alkylphosphonothioates of this invention a particularly useful group are the O-(4-cyanophenyl) alkylphosphonothioates of the formula wherein R is an alkyl radical containing 1 to 2 carbon atoms, and wherein R is phenyl (i.e., C H

The alkylphosphonothioates of this invention are eifective in destroying parasitic worm life in nematode intested soils. .For example O-phenyl O-(4-cyanopheny1) methylphosphonothioate at a concentration of 10 parts per million exhibited excellent control of the vinegar eel worm (both larvae and adults), Turbazrz'x acetz'. The soil phase of other nematode parasites is also controlled by incorporation in the nematode infested soil a nemavtocidally toxic amount of any of the alkylphosphonothioates of this invention.

The alkylphosphonothioates of this invention are eflective against a wide variety of insects and as illustrative of their activity but not limitative thereof is the followang:

A rimless, 25 x 200 mm. culture tube is rinsed with acetone and is placed in a holding block. The tube is filled with 50 cc. of distilled water. Next 0.1 gram of O-phenyl O-(4-cyanophenyl) methylphosphonothioate is dissolved in acetone to make a 1% by Weight concentrate of the compound. 0.05 ml. of this concentrate is pipetted into the culture tube containing the distilled water. The tube is then stoppered with an acetone washed rubber stopper and shaken vigorously to facilitate complete mixing. Approximately 25 early fourth instar yellow fever mosquito larvae (A'des aegyptl) are transferred to the tube with the aid of a pipette. The larvae are held in the test tube at room temperature for 24 hours at which time mortality observations are taken. This procedure is repeated at decreasing concentrations until a hill is observed. A 100% kill was observed at a concentration of 0.4 part per million.

A 1% by Weight concentrate is prepared by dissolving O-phenyl O-(4-cyanophenyl) methylphosphonothioate in 10 ml. of acetone. A 0.25 cc. tuberculin, B-D Yale syringe is filled with this concentrate and placed in a microinjection apparatus. The injector lever is pressed several times to make certain no air bubbles are trapped in the needle and the needle is wiped with filter paper to remove any excess solution. The injector lever is pressed once to deliver one microliter which is applied directly to each of 12 Lima bean leaf discs 0.25 inch in diameter. Individual second instar southern armyworm larvae (Prodenia eridania) are placed on each disc and the disc encaged with a plastic cap. After 48 hours at room temperature mortality observations are made. This procedure is repeated at decreasing concentrations and until a 100% kill is observed. A 100% kill was observed at a concentration of 0.02% by Weight.

A 1% by weight concentrate of O-phenyl O-(4-cyano phenyl) methylphosphonothioate is prepared by dissolving the chemical in ml. of acetone. A 0.25 cc. tuberculin, B-D Yale syringe is filled with the concentrate and placed in a microinjection apparatus. The injector lever is pressed several times to make certain that no air bubbles are trapped in the needle and the needle is wiped with filter paper to remove any excess solution. The injector lever is pressed once to produce one microliter which is applied directly to the ventral side of the abdomen of each of 10 plum curculio (Conotrachelus nenzzphar). After application each insect is released within observation dishes and held for 24 hours at room temperature and mortality observations made at the end of that time. This procedure is repeated at decreasing concentrations until a 100% kill is observed. A 100% kill was observed at a concentration of 0.05% by weight.

Although the alkylphosphonothioates of this invention are useful per se in controlling a wide variety of insect and nematode pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.

In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the alkylphosphonothioates of this invention are dispersed, it means that particles of the alkylphosphonothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semi-solid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g., pellets, granules, powders, or dusts. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the alkylphosphonothioates of this invention in a carrier such as dichloro-difluoromethane and the like fiuorochloroalkanes which boil below room temperature at atmospheric pressure.

In the instant specification and appended claims it is to be understood that the expression extending agent includes any and all of those substances in which the alkylphosphonothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g., pellets, granules, dusts and powders.

The exact concentration of the alkylphosphonothioates of this invention employed in combatting or controlling insect pests and nematode pests can vary considerably provided the required dosage (i.e., toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g., as in solutions, suspensions, emulsions, or aerosols) the concentration of the alkylphosphonothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semisolid or solid, the concentration of the alkylphosphonothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared pesticidal spray or particulate solid. In such a concentrate composition, the alkylphosphonothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well known insecticidal or nematocidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent), surface-active clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.

There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the alkylphosphonothioates of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanoue, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g., those boiling almost entirely under 400 F. at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytotoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.

When the alkylphosphonothioates of this invention are to be supplied to the pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifiuoromethane or like chlorofiuoroalkane which boils below room temperature at atmospheric pressure.

The alkylphosphonothioates of this invention are preferably supplied to the insect or nematode pests or to the environment of the pests in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the ialkylphosphonothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactant as employed here and in the ap pended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agen to connote generioally the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition, page 280). These surfactants include the Wellknown capillary-active substances which may be anionaotive (or anionic), cation active (or cationic), or nonionizing (or non-ionic) which are described in detail in volume I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, -Inc., New York) and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents, by John W. Mc- Cutcheon, and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles wit-11' respect to surfactants, i.e. the anion-active, cation-active and non-ionizing capillary active substances, are incorporated in this specification by reference in order -to avoid unnecessary enlargement of this specification.

The preferred surfactants are the water-soluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). :In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.

The alkylphosphonotthioates of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the insect or nematode pests environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentouite, fullers earth, pyrophyllite diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the absorbent clays, e.g., bentonite. These mixtures can be used for pesticidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.

For special purposes the alkylphosphouothioates of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promotors and/or surfactants or dispersing agents.

In all of the forms described above the dispersions can be provided ready for use in combatting insect or nematode pests or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concentrate is an intimate mixture of alkylphosphonothioate of this invention with a water-soluble surfactant which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with sufiicient of the alky-lphosphonothioate of this invention to make 100 parts by Weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of insect or nematode pests by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of Oaphenyl O- (4-cyanophenyl) methylphosphonothioate and 5 parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan mouolaurate.

Another useful concentrate adapted to be made into a spray for comb-atting a variety of insect or nematode pests is a solution (preferably as concentrated as possible) of an alkylphosphonothioate of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to percent by weight of the weight of the new pesticidal agent) of a surfactant (or emulsifying agent), which suifactant is also water-soluble. As illustrative of such a concentrate is a solution of O- phenyl O-(4-cyanophenyl) ethylphosphonothioate in benzene which solution contains dissolved therein a watersoluble polyoxyethylene glycol non-ionic surfactant and a Water-soluble alkylaryl sulfonate anionic surfactant.

Of the surfactants aforementioned in preparing the various emulsifiable, wettable or dispersible compositions or concentrates of this invention, the anionic and nonionic surfactants are preferred. Of the anionic surfactants, the particularly preferred are the well known water-soluble alkali metal alkylaryl sul-fonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly preferred are the water-soluble polyoxyethylene derivatives of .alkylphenols' (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters fo hexitol anhydrides (e.g., sorbitan). These materials in general 8 contain 15 to 30 moles of ethylene oxide per mole of .the hexitol anhydride or the alkylphenol.

In all of the various dispersions described hereinbefore for insecticidal or nematocidal purposes, the active ingredient can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, fungicides, bactericides, and herbicides. In this manner it is possible to obtain mixtures which are eifective against a wide variety of pests and other forms of noxious life.

In controlling or combatting insect or nematode pests the alkylphosphonothioates of this invention either per se or compositions comprising same are supplied to the insect or nematode pests or to their environment in a lethal or toxic amount. This can be done by dispersing the new pesticidal agent or pesticidal composition comprising same in, on or over an infested environment or in, on or over an environment the pests frequent, e.g., agricultural soil or other growth media or other media infested with the pests or attractable to the pests for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the insect or nematode pests and the alkylphosphonothioates of this invention. Such dispersing can be brought about by applying sprays or particulate solid compositions to a surface infested with the insect or nematode pests or attractable to the pests, as for example, the surface of an agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g., power clusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new pesticidal agent per se or pesticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the pests frequent, or by employing a liquid carrier for the new pesticidal agent to accomplish sub-surface penetration and impregnation therein.

While this invention has been described with respect to certain embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit and scope thereof.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. O-cyanoaryl alkylphosphonothioates of the formula wherein R is an alkyl radical containing 1 to 2 carbon atoms and wherein R is an aromatic hydrocarbon radical of the benzene series containing 6 to 7 carbon atoms.

3. O-(4-cyanophenyl) alkylphosphonothioates of the formula wherein R is an alkyl radical containing 1 to 2 carbon atoms and wherein R is phenyl.

4. O-phenyl O-(4-cyanophenyl) methylphosphonothioate.

5. O-phenyl O-(4-cyanophenyl) ethylphosphonothioate.

6. O-(o-tolyl) O-4-cyanophenyl) methylphosphonothioate.

7. O-(m-tolyl) O-(4-cyanophenyl) methylphosphonothioate.

8. A pesticidal composition comprising a compound of claim 1 dispersed in an extending agent.

9. A pesticidal composition comprising a compound of claim 1 dispersed in an extending agent selected from the group consisting of solid and semi-solid extending agents, the composition containing 0.1 to 25 percent by weight of said compound of claim 1.

10. A pesticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to 50 percent by Weight of said compound of claim 1.

11. A pesticidal concentrate comprising a compound of claim 1 and an insecticidal adjuvant, said concentrate containing from 5 to 95 percent by Weight of the compound of claim 1.

12. A pesticidal concentrate comprising a compound of claim 1 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant,

said concentrate forming an emulsion with water upon agitation therewith.

13. A pesticidal concentrate adapted to be made into a sprayable composition by the addition of Water comprising a compound of claim 1 in admixture with a watersoluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suificient of said compound of claim 1 to make 100 parts by weight.

14. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 1.

15. The method for protection of plants against insect attack which comprises applying to the plant an insecticidal amount of a compound of claim 1.

16. The method of controlling nematodes which comprises contacting the nematodes with a toxic amount of a compound of claim 1.

17. The method of destroying the soil phase of nematode parasites which comprises incorporating in the nematode infested soil a nematocidally toxic amount of a compound of claim 1.

No references cited. 

1. O-CYANOARYL ALKYLPHOSPHONOTHIOATES OF THE FORMULA 